PRODUCTION OF BIODIESEL FROM VEGETABLE OIL USING LYE

CERTIFICATE

This is to certify that Ishu Bala Thakur bearing Registration no. 10804787 has completed her capstone project titled, “Production of Biodiesel from Vegetable Oil using Lye ” under my guidance and supervision. To the best of my knowledge, the present work is the result of her original investigation and study. No part of the dissertation has ever been submitted for any other degree at any University.
The dissertation is fit for submission and the partial fulfillment of the conditions for the award of .........................

Signature and Name of the Research Supervisor: Miss Sugandha Bhatia
Designation:
School:
Lovely Professional University
Phagwara, Punjab.
Date :

DECLARATION

I, Ishu Bala Thakur , student of B.Tech (Hons.) Biotech under Department of
Lovely Faculty Of Technology and Sciences of Lovely Professional University, Punjab, hereby declare that all the information furnished in this capstone project report is based on my own intensive research and is genuine.
This report does not, to the best of my knowledge, contain part of my work which has been submitted for the award of my degree either of this university or any other university without proper citation.

Date : Signature and Name of the student :

Ishu Bala Thakur

Registration No.:10804787

ACKNOWLEDEMENTS

Working this project is great fun as this topic is of my interest. Working on this topic is adding a lot to my current knowledge. I am highly thankful to university who added this course (capstone project) to our degree & to my mentor Miss Sugandha Bhatia who is helping me a lot in working on this project.

CONTENTS

1.Introduction

2. Literature Review

3. Objective of the project

4.Materials

5. Procedure

6. Discussion

7.References

INTRODUCTION

Biodiesel is a new, alternative, renewable, clean diesel fuel made from Natural triglycerides - oils, fats, waste cooking oils and many other natural products.

Biodiesel is an alternative diesel that can be directly used in your diesel engines. It has a high level of viscosity which makes it a great lubricant in diesel engines than your regular petroleum diesel. It also reduces emission levels drastically, making biodiesel the best of its kind biofuel for a greener and better environment. Industry manufactured biodiesel is available for sale in fuel pumps. You can also try making biodiesel at home. The process is simple and can be accomplished with home equipments itself.
Principle: The principle behind biodieseling is to take vegetable oil (either new or used), and process it into a fuel that’s thin enough to spray from a regular diesel engine’s fuel-injection system. This is done chemically, by converting the oil into two types of compounds: biodiesel, which shares the original oil’s combustibility, and glycerin, which retains the oil’s thick, viscous properties. Drain away the glycerin, and you’re left with a fuel that you can pour into any diesel vehicle with no further modification.

The reaction may be named as transesterification or alcoholysis substitutes methanol (wood alcohol) for the Glycerol in triglycerides (fats, oils) to make the methyl esters called biodiesel. It uses lye as a catalyst.

Once you get to the far side of the learning curve, making biodiesel is very much like cooking. In fact, a commercial biodiesel production plant shares more in common with a large-scale bakery than a petroleum refinery.

Objective of the project

To prepare pure biodiesel from vegetable oil using lye (NaOH) by overcoming all the problems which arises during the process. Perform its washing and soponification And to collect recent information related to the topic and about its future perspectives.

LITERATURE REVIEW

Biodiesel is a fuel that can be used directly in any diesel engine generally without modification. It’s viscosity is twice that of regular diesel fuel which means it is better at lubricating your diesel engine than regular diesel. And emissions are cut dramatically vs using standard diesel fuel.

To produce biodiesel requires an alkaline catalyst, lye (sodium hydroxide or potassium hydroxide) to enable the reaction of methanol (methyl alcohol) and vegetable oil. Virgin oil of any type requires an amount of lye equal to about 1.0% by weight of the vegetable oil. This amounts to 3.5 grams of lye per liter of vegetable oil.( (Michael E. and Wayne P,2001) .

Vegetable oil is a triglyceride, which means that its molecule consists of a glycerin “backbone” with three fatty acids attached, forming a shape like a capital letter E. To make biodiesel, we add lye and methanol. (Ronald.K et.al,1998)

The highly caustic lye breaks the three fatty acid branches off of the glycerin backbone. These free fatty acids then bond with the methanol, which turns them into fatty acid methyl esters — otherwise known as biodiesel. The freed glycerin, which is heavier, sinks to the bottom, leaving the fuel (and lye) on top. Wash the lye out of the upper layer, and you have pure biodiesel.

Lye is an important ingredient in the making of biodiesel. This is because it is lye that breaks down the fatty acids from the waste vegetable cooking oils and separates the glycerin from the biodiesel mixture.(William Neilson, 2004)

Methanol is used to form sodium Methoxide with lye to be used in the process.(William Neilson, 2004)
REACTION INVOLVED:
Transesterification: Triglycerides (1) are reacted with an alcohol such as ethanol (2) to give ethyl esters of fatty acids (3) and glycerol (4): [pic]

Animal and plant fats and oils are typically made of triglycerides which are esters containing three free fatty acids and the trihydric alcohol, glycerol. In the transesterification process, the alcohol is deprotonated with a base to make it a stronger nucleophile. Commonly, ethanol or methanol are used. As can be seen, the reaction has no other inputs than the triglyceride and the alcohol.
The lye converts a small amount of the oil to soap so that the methanol will be soluble in the triglyceride. After the reaction is over, the glycerol and soap settle to the bottom of the vessel and the biodiesel floats on top.
After a quantity of biodiesel fuel is produced it will require washing or some other treatment to remove soap contamination. It can be tested for soap content by performing the Soap Test Titration. This test can help predict how a given batch of biodiesel will wash. It is also employed by those who use magnasol or synthetic magnesium silicate instead of water washing to determine how much magnasol to add.
Soap Test Titration:
The soap test titration uses hydrochloric acid, 0.01N solution, as a reagent, bromphenol blue, 0.4% aqueous, as a pH indicator, and acetone or isopropyl alcohol as a solvent. Bromphenol blue turns yellow at about 4.5. The yellow end point is the point at which all the soap in a test sample has been neutralized by the hydrochloric acid titrant. By knowing the volume of .01N HCl used in the soap test titration, it is possible to calculate the amount of soap in the biodiesel test sample.
Use the following formula:
Soap content (in ppm) = (ml of .01N HCL solution) / weight of sample x 30.44. (Liliana N. Ceci and Jorge E,2005
Problems which may arise: 1) But it’s not that simple. With some triglyceride molecules, only one or two fatty-acid branches break off, which leaves mono- or di-glyceride molecules (shaped like capital Ts or Fs), rather than free glycerin. At the same time, mixing methanol and lye produces some water — and oil, water, and lye mixed together make soap. With all of these incomplete and competing chemical reactions, your batch will inevitably contain soap, water, leftover lye, methanol, and mono- and di-glycerides, along with the nice biodiesel and glycerin. Mono- and di-glycerides are emulsifiers, so they prevent mixed liquids from separating, making it harder to extract biodiesel. 2) The picture gets even muddier when you use waste vegetable oil rather than pure oil, since it contains free fatty acids, water, and countless random contaminants from all those French fries. These by-products are bad for an engine, potentially causing micro-abrasions that damage fuel injectors or clog fuel filters. But you can remove them by washing or cooking the biodiesel in various ways, or by processing the incompletely converted biodiesel again, as if it were vegetable oil. In extreme cases, you’ll end up with a thick, soapy mass that never separates. All biodieselers wind up with a batch of this glop sooner or later. Fortunately, you can use it to make a good, grease-cutting soap — which is something that all biodiesel homebrewers need to have on hand.

3) Biodiesel will run in any diesel engine unmodified. Biodiesel is a solvent, so if you put it in an old tank or use it with a diesel engine that has been running regular diesel, it may clean and dissolve some "residues" and then the residues will clog your fuel filter. Changing the filter often when you first start using biodiesel usually fixes this problem. Usually, manufacturers warranties are not voided when biodiesel is used, but check with your manufacturer to make sure. Sometimes a blend like B20 is required (20% biodiesel). Now if you are running straight vegetable oil (SVO), then you need to make modifications to pre-heat the oil to decrease it’s viscosity.

4) The only other problem you might have is with natural rubber gaskets and hoses in vehicles made prior to 1992. The biodiesel may degrade these types of rubber and they may need replacing after a while. Newer engines have been modified (synthetic rubber) to stand up to the newer blends of diesel fuel that have been in use since 1992 and these engines will work fine with biodiesel.

MATERIALS REQUIRED

Equipments: 1) 2-liter bottle (plastic or larger; favor juice, water, or milk bottles over soda, since their wider mouths are easier to funnel into). 2) Bucket 3) Candy thermometer, Electric burner( not gas or hotplate). 4) Funnel, Glass jars (3 or more),Gloves ,Marker for labeling ,Mason jar (2), 1-pint, glass, with tight lids ,Measuring cup or beaker, or other way of measuring 220ml and one liter of liquid ,Pot- 2-liter 5) Metric gram scale, sensitive to at least ½ gram 6) Rags( clean),Safety goggles, Spoon(plastic). 7) Syringes (2), calibrated in milliliters(Or eyedroppers or pipettes. They should each hold up to 10ml, and be marked in increments no larger than 2ml).

Reagents: 1) Vegetable oil. 2) Methanol gasoline treatment Such as Heet, which is in a yellow bottle. 3) Cheesecloth 4) Isopropyl alcohol gasoline treatment such as Iso-HEET, which is in a red bottle, or Pyroil brand 5) Lye You can use regular lye (sodium hydroxide, NaOH) .NaOH is widely available as Red Devil Lye drain cleaner Litmus strips or electronic pH meter (optional) 6) Phenolphthalein solution. 7) Masking tape or labels( for labeling) 8) Distilled water( Used for washing the fuel). 9) Vinegar( To neutralize discarded lye).

PROCEDURE

To determine the quantity of lye to use for your oil 1. Dissolve 1 gram lye in 1 litre of water. 2. Dissolve 1ml. of vegetable oil in 10 ml. Isopropyl Alcohol 3. Drop the lye solution into the oil mixture, one milliliter at a time. After each ml. ,check the pH level of the oil mixture. 4. Continue to add the lye solution into the oil solution, one ml. at a time until a pH of 8-9 is reached. 5. Write down how many ml. of the lye solution you needed. 6. To determine the proportions - add 3.5 to the number you wrote down. The result is the number of grams you need to catalyze each litre of oil.
To make your biodiesel 1. Measure a quantity of oil into a suitable container and heat to 120F. 2. In separate container mix Methanol (15% by weight or 17.2% by volume in relation to the quantity of oil you are processing) with lye (calculating the amount using the method outlined above). The lye must be added slowly as it will become extremely hot. The resulting mixture is Sodium Methoxide. 3. Add the mixture to the heated oil mix vigorously for about an hour. You may want to set up some kind of mechanical aid to do this, perhaps using cycle power. 4. Monitor the rate of separation by taking samples at ten minute intervals. 5. Stop mixing when it appears that the separation has stopped. Leave the mixture to cool and settle over night or for at least 8 hours.

[pic] 7. The free fatty acids (glycerin), will sink to the bottom forming a cloudy layer. On top will be your biodiesel (methyl esters), but before using it, any remaining soaps or salts should be removed (or they may cause engine damage). 8. Syphon the methyl ester into a separate clean container and add water. Gently stir the mixture then leave it to settle again. When the water has separated from the methyl esters, drain or syphon the water out from the bottom of the container.
[pic]
9. Repeat the process until the rinse water you are removing reaches a pH level of 6 to 7 and contains no soap bubbles. If white substances form at the bottom. or any bubbles form at the surface the liquid should be re-washed.
[pic]
10. If the liquid appears cloudy, then water is being retained. It should be reheated gently in order to make the water evaporate.

Washing

11. Use the bubblewash method, but no need to monitor pH anymore. Just add a little 10% phosphoric acid (H3PO4) to the washing water first, 10 millilitres per gallon (2-3 ml/litre).

12. If you are curious about the results of your wash, use ordinary litmus paper, it will tell you the rough pH level (acidity/alkalinity). The end result should be neutral (pH7) or just below neutral.

13. Use one-third the volume of water as the amount of biodiesel to be washed. Make sure both the water and biodiesel are roughly the same (room) temperature. Pour your biodiesel into the vessel with the water, throw in the aquarium stone and start the air pump. Let it bubble for 24 hours minimum.

14. Turn the pump off and let the mixture settle for half an hour. The water will fall to the bottom, turning completely white, and the fuel you made will be much lighter in colour now. Drain the water, repeat the procedure two more times. Remove the biodiesel from the vessel, taking care not to get any water with it.

15. Let the biodiesel stand for about three weeks and use only when it becomes crystal clear; take a sample in a large marmalade jar and wait until it is completely cleared. Put it on your window shelf and enjoy looking at it while it clarifies. (If you want quicker results, heat the biodiesel to 45 deg C, 113 deg F, and let it cool.)

By products produced:

Glycerin:

The glycerine produced is brown and usually turns to a solid below about 100 deg F (38 deg C). Glycerine from fresh oil often stays a liquid at lower temperatures.

Reclaimed glycerine can be composted after being vented for three weeks to allow residual methanol to evaporate off or after heating it to 150 deg F (66 deg C) to boil off any methanol content (the boiling point of methanol is 148.5 deg F, 64.7 deg C). The excess methanol can be recovered for re-use when boiled off if you run the vapors through a condenser.

Another way of disposing of the glycerine, though a great bit more complicated, would be to separate its components, mostly methanol, pure glycerine and wax. This is often accomplished by distilling it, but glycerine has a high boiling point even under high vacuum so this method is difficult.

The glycerine by-product makes an excellent industrial-type degreaser/soap. One way to purify it is heat it to 150 deg F (65.5 deg C) to boil off excess methanol, making it safe for skin contact (take precautions with fumes). Once the glycerine is back to a liquid the impurities sink to the bottom and the color will become a more uniform dark brown. This can be cut with water leaving it a tan color, less concentrated and softer and easier to handle when washing hands. Produced this way the degreaser could be sold in squeeze or pump dispensers.

Other ideas for disposing of the glycerine are breaking it down to usable methane gas, with a methane digester or, for a much wilder idea, it could be broken down with pyrolisis. Pyrolisis was used extensively to run cars on firewood in oil-scarce Europe and elsewhere during World War 2. The processor has a heat source that heats the fuel (wood or glycerine) in an airtight box without oxygen. This allows the fuel to release its methane while not allowing it to burn. The methane is trapped in an inflatable storage container or compressed into a tank. This is an area of biodiesel development that warrants further work.

Soap residue

Suspended in the biodiesel will also be some soapy residues. These are the result of Na+ ions from the sodium hydroxide (NaOH) reacting with water created when the methanol bonds with the ester chains along with any other water that was suspended.

If the reaction produces more than the usual amount of soap, this happens when lye comes into contact with water before it has a chance to react with the vegetable oil- in this case the excess water should have been boiled off first.

The part of the process where it's vital to keep all water out of the reaction is when making the sodium methoxide. Keep the blender and all utensils the lye comes in contact with as dry as possible. The chances of a good clean splitting of esters from glycerine with little soap by-product are much better on a warm dry summer day than on a damp winter day.
DISCUSSION
Instead of using methanol, you can use ethanol. Ethanol is less toxic than methanol and is considered a “greener” fuel than methanol. Ethanol is “grain alcohol” and is usually made from corn which makes it a renewable fuel. Methanol is highly toxic and is made from fossil fuels or it can be distilled from fermented wood. That’s why it’s often called “wood alcohol”. Also... you can use potassium hydroxide instead of sodium hydroxide. We will have to use 1.4 times as much potassium hydroxide as sodium hydroxide though.
Various problems discussed should be resolved during its production and use in engine.

Pure biodiesel is being produced that can be used as an alternative to the diesel in various engines. Waste by products are produced but you can remove them by washing or cooking the biodiesel in various ways, or by processing the incompletely converted biodiesel again, as if it were vegetable oil.
Two turbocharged engines fueled with different proportions of biodiesel and diesel, namely, B50 (50% biodiesel + 50% diesel) and B20 (20% biodiesel + 80% diesel), were chosen to conduct performance and emission tests on a dynamometer. The results of the study indicate that there was a slight increase in fuel consumption by 8% and a drop in power by 3% with the blends of biodiesel, compared with diesel, and that the best improvements in emissions of smoke, HC, CO and PM were 65%, 11%, 33% and 13% respectively, but NOx emission was increased. The study also shows that it is satisfied to fuel engines with the low proportion blends of the biodiesel, without modifying engines, in performance and emissions.( Ge YS.et.al,2005)

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• Park YM.et.al.(2009) Esterification of used vegetable oils using the heterogeneous WO3/ZrO2 catalyst for production of biodiesel.Bioresour Technol Vol 1(1) Pg 59-61.

• Ge YS.et.al(2005) Preparation of biodiesel from waste edible oils and performance and exhaust emissions of engines fueled with blends of the biodiesel. Huan Jing Ke Xue Vol26(3)Pg12-25

• Oliveira D.et.al.(2005) Optimization of alkaline transesterification of soybean oil and castor oil for biodiesel production. Appl Biochem BiotechnolVol 1(1) Pg 121-124:553-60.

• Saloua F.et.al.Methyl ester of [Maclura pomifera (Rafin.) Schneider] seed oil: biodiesel production and characterization.Vol 101(9) Pg 3091-6.

• Michael E. & Wayne P. (2001) Factors that influence the production of biodiesel from vegetable oil. Journal of pharmacy researches Vol 3(9) Pg.123-144. • Liliana N et.al.(2005) use of lye in biodiesel production. Journal of Agricultural Technology 2010 Vol.6(1) Pg.149-158.. • Rob Elam .(2001) Biodiesel from Lye\Making biodiesel with lye 12 foolproof guidelines to follow NaOH. World J. Agric. Sci Vol (3)Pg. 839-843. • Enemuor.et.al.(1998) Biodiesel from Lye\Biodiesel Titrations. BP sciences Vol 6(5)Pg. 67-89

• William Neilson(2004) Biomass Energy Foundation Biodiesel. Biomade Vol Pg.678-698